1-octene composition

ABSTRACT

The present invention relates to a 1-octene composition. The 1-octene composition according to the present invention is prepared by ethylene oligomerization and comprises a high content of 1-octene and monomers useful for copolymerization of 1-octene at the same time.

CROSS-REFERENCE TO RELATED APPLICATION(S)

This application is a National Stage Application of InternationalApplication No. PCT/KR2015/009739, filed Sep. 16, 2015, and claims thebenefit of Korean Patent Application No. 10-2015-0125688 filed Sep. 4,2015, and Korean Patent Application No. 10-2015-0077366 on Jun. 1, 2015,the contents of which are incorporated by reference in their entiretyfor all purposes as if fully set forth below.

TECHNICAL FIELD

The present invention relates to a 1-octene composition which isprepared by ethylene oligomerization and comprises a high content of1-octene and monomers useful for copolymerization of 1-octene at thesame time.

BACKGROUND OF ART

Linear alpha-olefin is widely used in important commercial substancessuch as comonomers, detergents, lubricants, plasticizers or the like,and in particular, 1-hexene and 1-octene are commonly used as comonomersfor controlling density of polyethylene during preparation of linear lowdensity polyethylene (LLDPE).

In the conventional preparation process of LLDPE (Linear Low-DensityPolyethylene), copolymerization of ethylene with alpha-olefin, forexample, a comonomer such as 1-hexene and 1-octene is carried out inorder to control density by forming branches in the polymer backbone.

Therefore, there is a problem that the production cost of LLDPE having ahigh content of comonomers is high. Various methods have been tried tosolve this problem.

Further, because the application field or market size depends on thetype of alpha-olefin, a technique capable of selectively producing aparticular olefin is commercially important. Recently, many studies havebeen conducted on chromium catalysts for preparing 1-hexene or 1-octenewith a high selectivity through selective ethylene oligomerization.

The conventional commercial methods for preparation of 1-hexene or1-octene are the SHOP process of Shell Chemical, and the Ziegler Processof Chevron Philips, which are used to produce alpha-olefins with a widedistribution ranging from 4 to 20 carbons.

A chromium-based catalyst for ethylene trimerization having a ligand ofthe formula (R1)(R2)X—Y—X(R3)(R4) has been suggested, in which X isphosphorus, arsenic or antimony, Y is a linking group such as —N(R5)-,and at least one of R1, R2, R3 and R4 has a polar substituent or anelectron donating substituent.

Further, studies have been conducted on(o-ethylphenyl)₂PN(Me)P(o-ethylphenyl)₂ as a ligand which shows nocatalytic activity for 1-hexene under catalytic conditions and has nopolar substituent in at least one of R1, R2, R3 and R4 (Chem. Commun.,2002, 858).

However, the prior ligands containing heteroatoms as described above arestill required to maintain their polymerization activity consistentlyduring reactions for producing 1-octene or 1-hexene and to have highselectivity.

Meanwhile, it is required to minimize production of by-products otherthan 1-octene to obtain pure 1-octene upon preparation of 1-octene byolefin oligomerization. However, production of by-products other than1-octene is unavoidable in practice. Since the kind and content ofby-products vary depending on the oligomerization catalyst, catalystswith high 1-octene selectivity must be used. However, some by-productsmay be incorporated in the polyolefin during polymerization and mayresult in improvement of physical properties. In this case, there is noneed of removing by-products during purification of oligomerizationproducts.

Accordingly, the present inventors have studied various catalyst systemsfor olefin oligomerization, and found that a catalyst system for olefinoligomerization as described below is used to improve 1-octeneselectivity and to produce by-products capable of improving physicalproperties of polyolefins when 1-octene is used as a comonomer in thepreparation of polyolefins, thereby completing the present invention.

DETAILED DESCRIPTION OF THE INVENTION Technical Problem

The present invention provides a 1-octene composition which is preparedby ethylene oligomerization and comprises a high content of 1-octene andmonomers useful for copolymerization of 1-octene at the same time.

Further, the present invention provides a catalyst system for ethyleneoligomerization, which is used to prepare the 1-octene composition.

Technical Solution

In order to solve the above objects, the present invention provides a1-octene composition comprising 90% by weight or more of 1-octene and0.01 to 10% by weight of three or more of compounds represented by thefollowing Chemical Formulae 1 to 4:

Preferably, the 1-octene composition according to the present inventioncomprises 0.1 to 1% by weight of three or more of the compoundsrepresented by Chemical Formulae 1 to 4.

The 1-octene composition according to the present invention may beprepared by a method comprising the step of multimerizing ethylene inthe presence of a catalyst system for olefin oligomerization, thecatalyst system comprising a ligand compound, a transition metal source,and a cocatalyst.

As used herein, the term ‘olefin oligomerization’ means polymerizationof a small number of olefins. When three olefins are polymerized, it isreferred to as trimerization. When four olefins are polymerized, it isreferred to as tetramerization. The process of polymerizing a smallnumber of olefins to form a low molecular weight material is generallyreferred to as multimerization. Particularly, in the present invention,the olefin oligomerization means selective preparation of 1-octene, as amain comonomer of LLDPE, from ethylene.

Selective olefin oligomerization is closely related to a catalyst systemused. A catalyst system used for olefin oligomerization comprises atransition metal source which functions as a main catalyst, and acocatalyst, in which the structure of the active catalyst may be changedaccording to the chemical structure of the ligand, thereby varyingolefin selectivity and catalytic activity as well as the kind andcontent of by-products.

Particularly, in the present invention, the catalyst system for olefinoligomerization described below is used, thereby preparing any one ofthe compounds represented by Chemical Formulae 1 to 4 as a by-product.Further, a product comprising an alpha-olefin mixture and a solvent,which is prepared by using the catalyst system for olefinoligomerization, may be applied to a proper distillation column toseparate a C8 liquid composition having a boiling point of 110 to 140°C. at atmospheric pressure. In particular, the product prepared by usingthe catalyst system according to the present invention has very highselectivity for 1-octene in the C8 composition, i.e., 90% by weight ormore. Preferably, the 1-octene composition according to the presentinvention comprises 99% by weight or more of 1-octene.

Preferably, the 1-octene composition according to the present inventionalso comprises all of the compounds represented by Chemical Formulae 1to 4.

According to an exemplary embodiment of the present invention, the1-octene composition according to the present invention comprises 99% byweight or more of 1-octene and less than 1% by weight of the compoundsrepresented by Chemical Formulae 1 to 4, and therefore, the compositionmay have high 1-octene selectivity and comprise by-products useful forpolyethylene polymerization.

The ligand compound of the catalyst system for olefin oligomerizationcomprises two or more of a group represented by the following ChemicalFormula 5 in the molecule, in which the two or more of the group arelinked via four carbon atoms by a group selected from the groupconsisting of an aliphatic group having 1 to 20 carbon atoms, analicyclic group having 3 to 20 carbon atoms, and an aromatic grouphaving 6 to 20 carbon atoms:

wherein R₁ to R₄ are each independently C₁₋₂₀ alkyl, C₂₋₂₀ alkenyl,C₆₋₂₀ aryl, C₇₋₂₀ arylalkyl, C₇₋₂₀ alkylaryl, or C₇₋₂₀ alkoxyaryl.

The ligand compound comprises two or more diphosphinoamine functionalgroups, which are linked to each other via four carbon atoms. A grouplinking the diphosphinoamine functional groups is a group selected fromthe group consisting of an aliphatic group having 1 to 20 carbon atoms,an alicyclic group having 3 to 20 carbon atoms, and an aromatic grouphaving 6 to 20 carbon atoms. Due to such structural feature, the ligandcompound may exhibit high oligomerization activity when applied to thecatalyst system for olefin oligomerization.

Further, there is no theoretical limitation, but a unique interactionoccurs between adjacent chromium active sites, due to the structuralfeature of the ligand compound, leading to partial production ofmethylenecyclopentane during oligomerization. In turn, this compound isreacted with ethylene to produce the compounds of Chemical Formulae 1 to4.

Preferably, the group linking the two or more groups via four carbonatoms is selected from the group consisting of the following ChemicalFormulae:

wherein * is a region binding with N of Chemical Formula 1,

Ra is each independently hydrogen, or C₁₋₅ alkyl,

m is an integer of 1 to 5,

n is an integer of 1 to 6, and

a plurality of Ra binding to one ring may be the same as or differentfrom each other.

Preferably, R₁ to R₄ of Chemical Formula 5 are phenyl.

Representative examples of the ligand compound are as follows:

Another example of the ligand compound to achieve the above objects maybe a ligand compound represented by the following Chemical Formula 6.

wherein R₅ to R₈ are each independently C₆₋₂₀ aryl, or C₇₋₂₀ alkylaryl,

R₉ and R₁₀ are each independently C₁₋₂₀ alkyl, with the proviso that R₉and R₁₀ are not the same as each other,

R₁₁ to R₁₃ are each independently hydrogen, C₁₋₂₀ alkyl, C₂₋₂₀ alkenyl,C₇₋₂₀ arylalkyl, C₇₋₂₀ arylalkenyl, C₃₋₂₀ cycloalkyl, C₃₋₂₀cycloalkenyl, C₉₋₂₀ arylcycloalkyl, C₉₋₂₀ arylcycloalkenyl, C₆₋₂₀ aryl,or C₇₋₂₀ alkylaryl.

Preferably, R₅ to R₈ are phenyl, or 3,5-dimethylphenyl.

Preferably, R₉ is methyl, and R₁₀ is ethyl.

Preferably, R₁₁ to R₁₃ are hydrogen.

Representative examples of the compound represented by Chemical Formula6 are as follows:

According to an exemplary embodiment of the present invention, when thecatalyst system for olefin oligomerization according to the presentinvention was used to multimerize ethylene, the compounds of ChemicalFormulae 1 to 4 were detected in the 1-octene composition as a product.

Further, when 1-octene is used as a comonomer of a polyethylenecopolymer, a part of the compounds of Chemical Formulae 1 to 4 may actin copolymerization, together with 1-octene, because they have doublebonds at their ends. In general, physical properties of anethylene/1-octene copolymer may be improved by partially modifying thestructure of the polymer through another comonomer, in addition to thecomonomer content. Therefore, when the 1-octene composition according tothe present invention is used as a monomer of the copolymer, physicalproperties of the polymer may be improved by the compounds of ChemicalFormulae 1 to 4 which are included in the 1-octene composition. On thecontrary, internal octenes (e.g., cis and trans isomers of 2-octene,3-octene, 4-octene) as another type of by-products of the 1-octenecomposition hardly act in copolymerization due to their sterichindrance.

Meanwhile, in the catalyst system for olefin oligomerization accordingto the present invention, a transition metal source functions as a maincatalyst, and it may be any one or more selected from the groupconsisting of chromium(III)acetylacetonoate,tris(tetrahydrofuran)chromium trichloride,chromium(III)-2-ethylhexanoate,chromium(III)tris(2,2,6,6-tetramethyl-3,5-heptanedionate),chromium(III)benzoylacetonate,chromium(III)hexafluoro-2,4-pentanedionate, and chromium(III)acetatehydroxide.

Further, in the catalyst system for olefin oligomerization, thecocatalyst may be one or more selected from the group consisting ofcompounds represented by the following Chemical Formulae 7 to 9:—[Al(R₁₄)—O]_(c)—  [Chemical Formula 7]

wherein R₁₄ is the same as or different from each other, and eachindependently a halogen radical, a hydrocarbyl radical having 1 to 20carbon atoms, or a halogen-substituted hydrocarbyl radical having 1 to20 carbon atoms, and c is an integer of 2 or more,D(R₁₅)₃  [Chemical Formula 8]

wherein D is aluminum or boron, and R₁₅ is the same as or different fromeach other, and each independently hydrogen or halogen, a hydrocarbylhaving 1 to 20 carbon atoms, or a halogen-substituted hydrocarbyl having1 to 20 carbon atoms,[L-H]⁺[Q(E)₄]⁻  [Chemical Formula 9]wherein L is a neutral Lewis base, [L-H]⁺ is a Bronsted acid, Q is boronor aluminium in the +3 oxidation state, and E is each independently anaryl group having 6 to 20 carbon atoms or an alkyl group having 1 to 20carbon atoms, in which one or more hydrogen atoms are substituted orunsubstituted with halogen, hydrocarbyl having 1 to 20 carbon atoms, analkoxy functional group or a phenoxy functional group.

Examples of the compound represented by Chemical Formula 7 may includemethylaluminoxane (MAO), ethyl aluminoxane, isobutyl aluminoxane, orbutyl aluminoxane.

Examples of the compound represented by Chemical Formula 8 may includetrimethylaluminium, triethylaluminium, triisobutylaluminium,tripropylaluminium, tributylaluminium, dimethylchloroaluminium,dimethylisobutylaluminium, dimethylethylaluminium,diethylchloroaluminium, triisopropylaluminium, tri-s-butylaluminium,tricyclopentylaluminium, tripentylaluminium, triisopentylaluminium,trihexylaluminium, ethyldimethylaluminium, methyldiethylaluminium,triphenylaluminium, tri-p-tolylaluminium, dimethylaluminiummethoxide,dimethylaluminiumethoxide, trimethylboron, triethylboron,triisobutylboron, tripropylboron, or tributylboron.

Examples of the compound represented by Chemical Formula 9 may includetriethylammoniumtetraphenylboron, tributylammoniumtetraphenylboron,trimethylammoniumtetraphenylboron, tripropylammoniumtetraphenylboron,trimethylammoniumtetra(p-tolyl)boron,tripropylammoniumtetra(p-tolyl)boron,triethylammoniumtetra(o,p-dimethylphenyl)boron,trimethylammoniumtetra(o,p-dimethylphenyl)boron,tributylammoniumtetra(p-trifluoromethylphenyl)boron,trimethylammoniumtetra(p-trifluoromethylphenyl)boron,tributylammoniumtetrapentafluorophenylboron,N,N-diethylaniliniumtetraphenyl boron,N,N-diethylaniliniumtetraphenylboron,N,N-diethylaniliniumtetrapentafluorophenylboron,diethylammoniumtetrapentafluorophenylboron,triphenylphosphoniumtetraphenylboron,trimethylphosphoniumtetraphenylboron,triethylammoniumtetraphenylaluminium,tributylammoniumtetraphenylaluminium,trimethylammoniumtetraphenylaluminium,tripropylammoniumtetraphenylaluminium,trimethylammoniumtetra(p-tolyl)aluminium,tripropylammoniumtetra(p-tolyl)aluminium,triethylammoniumtetra(o,p-dimethylphenyl)aluminium,tributylammoniumtetra(p-trifluoromethylphenyl)aluminium,trimethylammoniumtetra(p-trifluoromethylphenyl)aluminium,tributylammoniumtetrapentafluorophenylaluminiurn, N,N-diethylaniliniumtetraphenylaluminium,N,N-diethylaniliniumtetraphenylaluminium,N,N-diethylaniliniumtetrapentafluorophenylaluminium,diethylammoniumtetrapentafluorophenylaluminium,triphenylphosphoniumtetraphenylaluminium,trimethylphosphoniumtetraphenylaluminium,triphenylcarboniumtetraphenylboron,triphenylcarboniumtetraphenylaluminium,triphenylcarboniumtetra(p-trifluoromethylphenyl)boron ortriphenylcarboniumtetrapentafluorophenylboron.

The catalyst system for olefin oligomerization according to the presentinvention may have a mole ratio of the compound represented by ChemicalFormula 5 or 6: transition metal source: cocatalyst of about 1:1:1 toabout 10:1:10,000, preferably about 1:1:100 to about 5:1:3,000, so as toincrease 1-octene selectivity and multimerization activity. However, thepresent invention is not limited thereto.

In the catalyst system for olefin oligomerization comprising thecompound represented by Chemical Formula 5 or 6, the transition metalsource, and the cocatalyst, the three components may be addedsimultaneously or sequentially in a random order to a suitable solventin the presence or absence of monomers, and they may be obtained as anactive catalyst. The suitable solvent may include heptane, toluene,1-hexene, diethylether, tetrahydrofuran, acetonitrile, dichloromethane,chloroform, chlorobenzene, methanol, acetone, or the like, but is notlimited thereto.

The present invention also provides a method of preparing an olefinoligomer, the method comprising the step of multimerizing olefins in thepresence of the catalyst system for olefin oligomerization. When thecatalyst system for olefin oligomerization according to the presentinvention is used, a method of oligomerizing olefin with improvedreaction activity and selectivity may be provided. Preferably, theolefin is ethylene.

The olefin oligomerization according to the present invention may beconducted as a homogeneous liquid phase reaction, a slurry reaction, inwhich a catalyst system is not dissolved in part or in whole, atwo-phase liquid/liquid reaction, or a bulk phase reaction or a gasphase reaction, in which a product olefin acts as a main medium, in thepresence or absence of an inert solvent, using the catalyst system forolefin oligomerization and a common device and contact technology. Thehomogeneous liquid phase reaction is preferred.

The olefin oligomerization may be conducted in any inert solvent thatdoes not react with a catalyst compound and an activator. The suitableinert solvent may include benzene, toluene, xylene, cumene, heptane,cyclohexane, methylcyclohexane, methylcyclopentane, hexane, pentane,butane, isobutane, or the like, but is not limited thereto. In thisregard, the solvent may be treated with a small amount of alkylaluminumto remove a small amount of water or air acting as a catalyst poison,before use.

The olefin oligomerization may be conducted at a temperature of about 5°C. to about 200° C., preferably about 30° C. to about 150° C. Further,the olefin oligomerization may be conducted at a pressure of about 1 barto about 300 bar, preferably about 2 bar to about 150 bar.

Advantageous Effects

A 1-octene composition according to the present invention is prepared byethylene oligomerization and comprises a high content of 1-octene andmonomers useful for copolymerization of 1-octene at the same time.

BRIEF DESCRIPTION OF DRAWINGS

FIG. 1 shows the result of analyzing an octene composition prepared inan exemplary embodiment of the present invention.

DETAILED DESCRIPTION OF THE EMBODIMENTS

Hereinafter, the present invention will be explained in more detail withreference to the following Examples. However, these Examples are only toillustrate the invention, and the scope of the invention is not limitedthereto.

Hereinafter, all the reactions were progressed using a Schlenk techniqueor a Glove box under an argon atmosphere. The synthesized compounds wereanalyzed by ¹H (500 MHz) and ³¹P (202 MHz) NMR spectra using a Varian500 MHz spectrometer. Shift was expressed in ppm, downfield from TMS,with a residual solvent peak as a reference. A phosphorous probe wascalibrated with aqueous H₃PO₄.

Preparation Example 1

Under an argon atmosphere,3-(aminomethyl)-3,5,5-trimethylcyclohexaneamine (5 mmol) andtriethylamine (3-10 equivalents) were dissolved in dichloromethane (80mL). While the flask was immersed in a water bath,chlorodiphenylphosphine (20 mmol) was slowly added, and the mixture wasstirred overnight. The solvent was removed under vacuum, and then THFwas added, the mixture was sufficiently stirred, and triethylammoniumchloride salt was removed with an air-free glass filter. The solvent wasremoved from the filtrate to obtain a target compound.

³¹P NMR (202 MHz, CDCl₃): 45.6 (br s), 56.2 (br s)

Preparation Example 2

Under an argon atmosphere, 2-ethyl-6-methylaniline (10 mmol) andtriethylamine (3 equivalents) were dissolved in dichloromethane (80 mL).While the flask was immersed in a water bath, chlorodiphenylphosphine(20 mmol) was slowly added, and the mixture was stirred overnight. Thesolvent was removed under vacuum, and then THF was added, the mixturewas sufficiently stirred, and triethylammonium chloride salt was removedwith an air-free glass filter. The solvent was removed from the filtrateto obtain a target compound.

³¹P NMR (202 MHz, CDCl₃): 59.2 (br s)

Preparation Example 3

Under an argon atmosphere, 2-ethyl-6-methylaniline (10 mmol) andtriethylamine (3 equivalents) were dissolved in dichloromethane (80 mL).While the flask was immersed in a water bath,chlorobis(3,5-dimethylphenyl)phosphine (20 mmol) was slowly added, andthe mixture was stirred overnight. The solvent was removed under vacuum,and then THF was added, the mixture was sufficiently stirred, andtriethylammonium chloride salt was removed with an air-free glassfilter. The solvent was removed from the filtrate to obtain a targetcompound.

³¹P NMR (202 MHz, CDCl₃): 57.2 (br s)

Example 1

Step 1

Under argon gas, Cr(acac)₃ (17.5 mg, 0.05 mmol) and the compoundprepared in Preparation Example 1 (0.025 mmol) were added into a flask,methylcyclohexane (100 mL) was added, and the mixture was stirred toprepare a 0.5 mM solution (based on Cr).

Step 2

Vacuum was applied to 600 mL-Parr reactor for 2 hours at 120° C., thenthe internal atmosphere was replaced with argon, and the temperature waslowered to 60° C. 175 mL of methylcyclohexane and 2 mL of MMAO(isoheptane solution, Al/Cr=1200) were added, and 5 mL of 0.5 mMsolution (2.5 umol) was added into the reactor. The mixture was stirredat 500 rpm for 1 minute, a valve of an ethylene line adjusted to 60 barwas opened to fill the inside of the reactor with ethylene, and then thetemperature was controlled to 60° C. and the mixture was stirred at 500rpm for 15 minutes. The ethylene line valve then was closed, the reactorwas cooled to 0° C. with a dry ice/acetone bath, non-reacted ethylenewas slowly vented, and 0.5 mL of nonane (GC internal standard) wasadded. After stirring for 10 seconds, 2 mL of the liquid part of thereactor was taken and quenched with water, and the organic part wasfiltered with a PTFE syringe filter to make a sample. The sample wasanalyzed by GC-MS and GC-FID as in the following Experimental Example,and quantified by GC-FID.

Step 3

400 mL of ethanol/HCl (10 vol %) was added to the remaining reactionsolution, and the mixture was stirred and filtered to obtain a polymer.The obtained polymer was dried overnight in a vacuum oven at 65° C., andthe weight was measured.

Example 2

The same process as in Example 1 was conducted to prepare a sample and apolymer, except that the compound prepared in Preparation Example 2(0.05 mmol) was used instead of the compound prepared in PreparationExample 1.

Example 3

The same process as in Example 1 was conducted to prepare a sample and apolymer, except that the compound prepared in Preparation Example 3(0.05 mmol) was used instead of the compound prepared in PreparationExample 1.

Example 4

The same process as in Example 1 was conducted to prepare a sample and apolymer, except that the compound prepared in Preparation Example 2(0.05 mmol) was used instead of the compound prepared in PreparationExample 1 and n-heptane was used instead of methylcyclohexane as asolvent.

Comparative Example 1

1-Octene (98%, 04806-1L) purchased from Sigma-Aldrich was used asComparative Example 1.

Comparative Example 2

1-Octene purchased from INEOS was used as Comparative Example 2.

Comparative Example 3

The same process as in Example 1 was conducted to prepare a sample and apolymer, except that a catalyst system prepared from Cr(acac)₃,Ph₂PN(iPr)PPh₂ and MMAO according to the literature (J. Am. Chem. Soc.2005, 127, 10723-10730) was used.

Experimental Example

GC-FID analysis was conducted using 1-octene compositions of Examplesand Comparative Examples as follows.

AT-5 column (0.32 mm ID×30 mL) was used, and gases such as Column (He)1.6 mL/min, Make-up (He) 30 mL/min, Hydrogen 40 mL/min, and Air 400mL/min were applied and analyzed. During analysis, the program was asfollows: the temperature of an oven was maintained at 35° C. for 5minutes, and then raised at a rate of 1° C./min. At a moment when thetemperature reached 50° C., the temperature was raised at a rate of 15°C./min. The temperature was maintained at 300° C. for 30 minutes andthen terminated. Analysis was conducted at an injector temperature of270° C., at a detector temperature of 280° C., and at an injector splitof 25/1 with an injection volume of 0.2 uL.

The analysis results are given in the following Table 1, together withthe catalytic activity.

TABLE 1 Catalytic 1-Hexene + C6 activity 1-Hexene 1-Octene 1-octeneisomers (ton/molCr/hr) (wt %) (wt %) (wt %) (wt %) Ex. 1 196 39.0 45.384.3 3.6 Ex. 2 161 49.5 40.5 90.0 1.5 Ex. 3 156 39.2 52.6 91.9 1.0 Ex. 4131 24.1 63.2 87.3 2.0

The C8 compositions or the compositions of by-products in Examples 1 to4 and Comparative Examples 1 to 3 are given in the following Table 2, inwhich the by-products appeared around 1-octene peak expected to have aboiling point of 110° C. to 140° C. under atmospheric pressure.

Further, GC chromatogram of Example 1 is shown in FIG. 1.

TABLE 2 GC-FID Products in C8 elution time Ex. 1 Ex. 2 Ex. 3 Ex. 4 Com.Com. Com. # composition (min) (wt %) (wt %) (wt %) (wt %) Ex. 1 Ex. 2Ex. 3 1 1-Octene 8.25-8.65 99.012 99.267 99.349 99.244 >98 wt % 85.7 —wt % 2 n-Octane 8.699 0.122 0.016 0.022 0.000 ◯²⁾ ◯ ◯ 3 2-Octene 8.8240.104 0.059 0.048 0.120 ◯ ◯ ◯ 4 2-Octene 8.942 0.026 0.019 0.035 0.000 ◯◯ ◯ 5 Chemical 9.186 0.218 0.153 0.229 0.094 X³⁾ X ◯ Formula 1 6Chemical 9.637 0.113 0.078 0.123 0.045 X X ◯ Formula 2 7 Chemical 10.0630.231 0.221 0.114 0.266 X X X Formula 3 8 Chemical 10.589 0.174 0.1870.079 0.232 Trace X X Formula 4 1 + 2 + 3 + 4¹⁾ 0.736 0.639 0.545 0.637Sum 100 100 100 100 ¹⁾Sum of Chemical Formulae 1 to 4 ²⁾detected³⁾undetected

The invention claimed is:
 1. A 1-octene composition comprising 90% byweight or more of 1-octene and 0.01 to 10% by weight of three or more ofcompounds represented by the following Chemical Formulae 1 to 4:


2. The 1-octene composition of claim 1 comprising 0.1 to 1% by weight ofthree or more of the compounds represented by Chemical Formulae 1 to 4.3. The 1-octene composition of claim 1 comprising 99% by weight or moreof 1-octene.
 4. The 1-octene composition of claim 1 comprising all ofthe compounds represented by Chemical Formulae 1 to 4.